Organothiophosphate derivatives of halogenated cyclic sulfones



United States Patent $228365 ORGANOTHIOPHUSPHATE DERIVATIVES 0F HALOGENATED CYCLIC SULFONES Sheldon B. Greenbaum, Tonawanda, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a

corporation of New York No Drawing. Filed Nov. 30, 1964, Ser. No. 414,832

4 Claims. (Cl. 260332.1)

This is a continuation-in-part of my application Serial No. 165,025, filed January 8, 1962.

This invention relates to novel organophosphorus derivatives of cyclic sulfones useful as pesticides. More particularly, this invention describes new organophosphorus derivatives of cyclic chlorinated or brominated sulfones having contact and systemic toxicity toward insects.

The compositions of this invention have the structure:

wherein the Rs are independently selected from the group consisting of a lower alkyl radical and X is bromine or chlorine. The alkyl radicals or groups herein may have from one to four carbon atoms and may be branched or unbranched. Preferred alkyls are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl. Mixtures of compound wherein both Rs are ethyl and the halogen is chlorine.

The terms insecticide and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect is used not only to include those small invertebrate animals belonging mostly to the class Insects, comprising six-legged, usually-winged forms such as beetles, bugs, bees, flies and so forth, but also to other allied classes of arthopods whose members are Wingless and may or may not have more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms, nematodes and the like.

The novel organophosphorus derivatives of cyclic sulfones of this invention offer several unexpected advantages over comparable or related compositions of the prior art. For example, the compositions of this invention are potent contact and systemic insecticides at low levels of concentration. Thus, the material can be applied to the root areas of plants and by absorption into the plants through the roots, the pests are controlled through contact with the plants. A specific method of systemic control is in the coating of seeds with the compounds of this invention prior to planting, and then allowing the seeds to germinate. In thisway the pesticide is absorbed into the seedling. Furthermore, this insecticidal activity persists for long periods of time after application. That these structures are insecticidal at all is both unexpected and surprising in view of the relative inactivity as insecticides of those compounds wherein X is hydrogen rather than any of the designated substituents. The fact that the presence of this hydrogen atom on this position of the molecule de-activates the compounds as insecticides is considered unusual. The activity of the compositions at these very low concentrations, particularly as contact insecticides, is most advantageous. This level of activity offers the obvious advantage of low cost use, as well as reducing the danger of mammalian toxicity.

An additional important advantage of the inventive ice compositions as insecticides is that they possess an unusually broad spectrum of activity. That is, the compositions are toxic to a wide variety of insects, including but not limited to flies, mosquitoes, roaches, beetles, silverfish, aphids, and mites. Many of the related compositions of the prior art are so specific in their insecticidal activity as to require the use of other insecticides to control the normal insect population encountered. This shortcoming often makes the prior art insecticides commercially unsuitable. By contrast, the compositions of this invention are especially suitable for crop and garden use where many different species of insects are commonly encountered.

An additional advantage of these novel compositions is that they may be utilized as pesticides in various grades of purity, ranging from a crude reaction mixture up to a highly refined product. Furthermore, these compositions may be combined with other pesticides, for example, insecticides, such as DDT, methoxychlor, lindane, aldrin, en-drin, DDD, BHC, parathion, malathion methyl parathion, lead and other metallic .arsenates, rotenone, allethrin, pyrethrum, nicotine, summer oils, dormant oils, petroleum fractions and distillates, dinitroalkylphenols, dinitrocresols, chlordane, heptachlor, chlorinated terpenes, demeton, other insecticidal organophosphates, thiophosphates and dithiophosphates such as those commercially designed as Guthion, Diazinon, Dibrom and others; miticides such as bis(pentachlorocyclopentadienyl), chlorinated arysulfonates, quinoxaline trithiocarbonates, chlorinated diarysulfones and the like, fungicides such as sulfur, dithiocarbamates and N-trichloromethylthio-4-cycloheXene-1,2-dicarboximide to list but a few.

It is also desirable to combine the insecticidal products of this invention with a class of potentiators or synergists known in the insecticidal art as knockdown agents.

These substances are materials which may or may not be insecticidal themselves, but which when combined with other insecticides will shorten the time required, or reduce the amounts of the insecticide necessary to effect total immobilization (knockdown) or death of the insect to be controlled. Among the large number of synergists which may be used for this purpose are the organic thiocyanates and the water-soluble organophosphates, such as Phosdrin and Sesoxane [2-(3,4-methylenedioxyphenoxy)6,6,9- trioxaudecane], among others.

Yet another advantage of the inventive compositions is that they may readily be formulated as solids or liquids using solid or liquid solvents, vehicles, carriers or extenders.

Suitable diluents are solids or liquids of an inert nature. Illustrative solid diluents include among many others: sawdust, clay, flours, silicas, alkaline earth carbonates, oxides and phosphates, sulfur and the like.

Suitable solvents for liquid formulations include ketones, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and petroleum fractions or distillates. Solutions in solvents such as these may be further dispersed in Water by use of emulsifiers.

Whether dissolved or dispersed, suspended or emulsified in a liquid or formulated as a dust or powder or some other solid preparation, the insecticides of this invention may advantageously contain one or more substances known or referred to variously as modifiers, wetting agents, surface active agents, dispersing agents, suspending agents, emulsifying agents, or conditioning agents, said materials being referred to herein generically as adjuvants. Thus, any substance which facilitates formulation, handling and application of the insecticide of this invention may be profitably incorporated in the insecticidal composition. Frequently, said adjuvants enhance or potentiate insecticidal effectiveness. A satisfactory but not exhaustive list of these substances appears among other places in Soap and Chemical Specialties, volume 31; No. 7, pages 50-61; No.8, pages 4861; No. 9, pages 52-67 and No. 10, pages 3867 (1955). Another source of this information is Bulletin 15-607 of the Bureau of Entomology and Plant Quarantine of the United States Department of Agriculture.

The insecticidal compositions of this invention may be applied as a dust or a spray using among other things, any of the above-mentioned exemplified formulations.

The preferred method of application is a spray using petroleum fractions or distillates as diluents plus one 01 more conditioning agents as formulation adjuvants. Ordinarily, a typical spray will contain between about 0.001 percent and about ten percent by weight of insecticide with the remaining material being made up largely of solvent with a small amount of adjuvant.

Inits process aspects, this invention offers the advantage of an economically feasible process for preparing most of the compositions of this invention in good yield from commercially available starting materials. This involves reacting 3-sulfolene with a di-lower-alkoxyphosphinyl sulfenylchloride or bromide. This reaction is set forth below:

wherein R is a lower alkyl radical of 1 to 4 carbon atoms, and X is a bromine or chlorine, preferably chlorine.

The reaction proceeds readily .at relatively wide ranges of temperatures, zero degrees to two hundred degrees centigrade, depending upon the reactivity of the reactants used. Where both reactants are liquids, the reaction may be effected without using diluents, although diluents such as inert aromatic or aliphatic hydrocarbons, ketones, or alcohols make for smoother reactions.-

EXAMPLE 1 Preparation of 0,0-diethyl S-(4-chl0r0-1,]-di0x0tetrahydr-3-thienyl) phosphorothioate A mixture of 11.8 grams of 2,5 -dihydrothiophene-1,1- dioxide (sulfolene) and forty milliliters of carbon tetrachloride is treated dropwise with'2'0'.5 grams of diethoxyphosphinyl sulfenyl chloride at room temperature. (The sulfenyl chloride was prepared according to the directions of Michalski et al., Chemistry and Industry, page 1199 (1958).) The sulfolene is relatively insoluble in the solvent at the start of the reaction. A one milliliter aliquot of supernatant fluid produces the equivalent of 10.8 milliliters of 0.1 N iodine from potassium iodide. The mixture is heated at reflux overnight and after cooling and removing the small amount of sulfolene remaining, one milliliter of the filtrate produces the equivalent of only 0.25 milliliter of 0.1 N iodine showing substantial completion of the reaction. The filtrate is reduced to dryness, the residue is taken up in benzene, washed with five percent sodium bicarbonate and again reduced to dryness to give a yellow oil.

Analysis.-Calculated for C H ClO PS P, 9.7 percent; Cl, 10.9 percent. Found: P, 10.0 percent; Cl. 11.0 percent.

0,0-diethyl S'- (4-chloro-1,1-dioXotetrahydro-3-thienyl) phosphorothioate is a newcompound; It is useful as an intermediatefor organic synthesis, especially in the preparation of pesticides, in addition to being .a very active dimethyl phosphinyl sulfenyl bromide, diisopropyl phosphinyl sulfenyl chloride, di-n-butyl phosphinyl sulfenyl bromide and methyl, ethyl phosphinyl sulfenyl chloride, the corresponding 0,0-di-lower-alkyl S-(4-halo-1,1-dioxotetrahydro-3-thienyl) phosphorothioates are made.

EXAMPLE 2 Formulations A typical emulsifiable concentrate made from the prodnot of Example 1 contains about 25 percent alkyl aryl sulfonates and polyoxyethylene sorbitan esters and an indifferent solvent such as xylene. The following is given for the purpose of illustration.

Parts 0,0-diet-hyl S-(4-chloro 1,1 dioxotetnahydro-3-th'- enyl) phosphorothioate 40 Atlox 3335 3 Atlox 89108 a. 1 Xylene 116 A typical granular fonmulation made from the above toxicant contains a carrier, toxicant and stabilizers:

. Parts 0,0-diethyl S-(4-chloro 1,1 dioxotetrahydro-3-thienyl) phosphorothioate 2 Urea mesh) 1 Attaclay LVM (30/60 mesh) 17 A typical seed coating made from the above toxicant contains a carrier such as carbon and a sticker such as methyl Cellosolve (trademark of Union Carbide Corporation for monoand di-alkyl ethers of ethylene glycol and their derivatives):

Parts 0,0-diethyl S-(4-chlor-o 1,1 dioxotetrahydro-3-thienyl) phosphorot-hioate 1 Darco G-60 3 Sticker solution of 2 percent aqueous methyl Cellosolve.

H ousefly tests Fifty adults of the CSMA (Chemical Specialties Manufacturers Association) strain are sprayed in a 2 inch x 5 inch diameter stainless steel cage faced on top and bottom with 14 mesh screen. Flies are retained in the cage in which they are sprayed for knockdown observations and 24 hour mortality determinations. Mortality which re sults from this test maybe from residual contact as well as by direct contact spray.

' The. active ingredients were employed as aqueous emulsions made from the emulsifiable concentrate of Example 2 (or comparable concentrate of comparative compound). The emulsion contained 0.1 percent active ingredient.

Spider mite tests Lima bean plants were infested with fifty to one hundred adults of the strawberry spider mite, Tetranychus atlanticus, prior to testing. The infested plants are dipped into the test material and held for five days. Adult mortality was noted. I

Systemic insecticidal activity is evaluated by applying 20 milliliters of the sample to the vermiculite substratum of potted pea plants. Forty-eight hours after application the plants are infested with mites and a mortality determi-- nation is made after five da'ys.

PERCENTAGE KILLED (GREENHOUSE NO. 1)

Mite (Tetranychua Housefly, atlamz'cus) 0.1% Cone.

Contact, Systemic, 0.1% Cone. 0.1% Conc.

El) CIUSP(O 02115): 88 100 90 fi -SP(QC2H5)z 0 38 0 L J J EXAMPLE 4 Mexican bean beetle tests Lima bean leaves sprayed on the dorsal and ventral surfaces are ofiered to larvae of the Mexican bean beetle 6 are then sprayed on a turntable with 100 milliliters of the chemical emulsion. Each plant is then caged in a Plexiglas piece of tubing supported by a thin aluminum plate and filter paper. The inside of the tube is coated with talcum powder to prevent escape of the aphids. Mortality is then recorded by counting the number of dead aphids and percent mortality determine from the total number.

Mexican bean beetle Primary leaves of lima bean plants are excised and dipped into solutions containing the chemicals. The leaves are allowed to dry by placing the petiole in water using 50 milliliter flasks. After they are dry, they are transferred to paper cups inserting the petiole through a small hole at the bottom of the cup. The petiole is then kept immersed in water to prevent wilting of the treated leaf. The cup serves then as a chamber for the leaf into which larvae (fourth instar) of the Mexican bean beetle (Epilachna varivestis Muls.) are inserted. The cup is covered with a Petri plate top to prevent escape of the insects. Mortality of the larvae is recorded after 48 hours.

RESULTS OF TESTING AGAINST APHIDS AND MEXICAN BEAN BEETLES AT GREENHOUSE #2 (late second instar) for a forty-eight hour feeding period. O The mortality data are recorded. H

Pea aphid tests C] SP(OCH5) Adult pea aphids are sprayed and transferred to sprayed pea plants and held for forty-eight hour mortality deterg minations.

Percent killed (at indicated concentrations of active compound) Insect Aphid 100 100 100 100 100 100 100 Mexican Bean Bettle 100 100 100 100 Systemic insecticidal activity is evaluated by applying the sample to the vermiculite substratum of potted pea plants. Forty-eight hours after application the plants are While I have given specific illustrations of compositions, intermediates therefor, processes for making these materials, and of certain uses therefor, in this specificainfested with ten adult pea aphids and mortality determition, it is to be understood that various other modificanation is made after five days.

PERCENT KILLED (GREENHOUSE #1) tions can be made by one of ordinary skill in this art Pea Aphid Mexican Bean Beetle, Concentration Contact Concen. Systemic Concen.

i (BUST-(O C2H5) z 100 60 100 100 50 26 i USP-(002E102 0 0 0 20 0 0 0 0 0 EXAMPLE 5 Spray tests (insecticides)-Aphid test Ten-day-old Nasturtium plants are infested with black bean aphids (aphis fabae Scop.) so that the two first Without departing from the scope of my invention and I do not want to be limited to same, except as defined in leaves have from 50 to 100 aphids. The infested plants 7 the appended claims.

7 8 What is claimed is: l 4.

' o SA -(001m H I I I S L I i References Cited by the Examiner S UNITED STATES PATENTS 7 10 2,393,925 1/1943 Morris et a1. 1 7-33 2,844,582 7/1958 Raley 260-489 7 2,882,278 4/1959 McConnell et a1. 260332.1 2,937,972 5/1960 Bluestone et a1 167+33 wherein X 1s a halggen selected from the group consistr 3 106,565 10/1963 Newanis ing of bromine and chlorine and the Rs independently represent lower alkyl. OTHER REFERENCES 2- A o p und c r ing o claim 1 wh ei X i Zemlicka et 211.: Chemical Abstracts, vol. 58 (1963), chlorine, page 5607.

3. A compound according to, claim 1 whereinfthe Rs are the same. 20 WALTER A. MODANCE, Primary Examiner. 

